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Rubber Elasticity*
G. GE~
In this review a modified equation [or the lree energy o[ a single chain is pro-
posed, based on a recent discussion of the excluded volume problem. A simple
model o[ a network element is used to study departures from affine behaviour
and the form of the stress/strain curve. Comparison with the Mooney equation
suggests that the C~ term cannot be explained in terms of excluded volume,
and it is suggested that the packing problem requires [urther study. Energy and
volume changes on elongation are reviewed and the need for [urther work
emphasized.
(1) Introduction
IT IS not possible, in the course of a single lecture, to review all facets of
the theory of rubber elasticity. Comments will therefore be centred on two
topics of current interest: (a) the form of the stress/strain curve, and its
dependence on chain statistics; (b) the volume and energy changes accom-
panying elongation.
The quantitative interpretation of rubber elasticity 1 rests firmly on the
use of Gaussian statistics to describe the behaviour of a single chain. The
elastic network is then treated as an assembly of chains, with the assumption
--which can be justified for Gaussian chains---of affine deformation of the
junction points. From time to time the suggestion has been made that some
of the observed discrepancies between theory and experiment may have their
origin in departures from Gaussian statistics. It is well known that a free
chain, in a neutral environment, is not Gaussian, due to the excluded volume
effect. In a dilute solution the overall dimensions depend upon the nature
of the solvent, and much use has been made of theta solvents, defined 2 as
those in which the laws of ideal solutions hold at finite (low) concentrations.
Under these circumstances the net excluded volume effect is zero, the expan-
sion due to this cause being balanced out by the contraction occurring in a
thermodynamically poor solvent. It is also generally accepted 3,4 that in a
bulk polymer, the effective excluded volume must be zero, because the
local structure is determined by interactions of segments, in which it is a
matter of indifference whether these belong to the same or to different
molecules.
Quantitative analysis of the behaviour of networks of non-Gaussian chains
raises two problems: (1) the description of the properties of a single chain,
and (2) the study of possible departures from affine deformation. In this
paper we make use of a recent treatment of the statistics of an infinite chain
to define a parameter which can be used to describe departures from Gaus-
sian statistics. The resulting free energy equation is then used in an accurate
study of a 'network' of four chains, where departure from affine behaviour
can be determined.
*This review was vrevared during the tenure of a Fellowship o f the Michigan Foundat/on for Advanced
Research, Midland, Michigan, U.S.A.. and was presented at the Great Lakes Conference on Polymer
and Colloid Science, Detroit, Michigan, U.S.A., October 1965.
373
G. GEE
where, for long chains, 022 2> y > 0"18. Schatzki 7 has also tabulated dis-
tributions of end to end distances, from which it is possible to derive
numerically 8 P(r) and W(r). These suffer from the fact that the particular
lattice model chosen necessarily imposes a certain discontinuity, although
Domb 9 has shown that all lattices give similar values of y (equation (5)).
Recently Edwards 1° has succeeded in obtaining an asymptotic solution in
closed form for the position of the nth link of an infinite chain, which may
374
THE PRESENT STATUS OF THE THEORY OF RUBBER ELASTICITY
be written
P(r) ~,~ exp [ - (1 "35/riP) (r - 0-87n°'6/a°'2) 2] (6)
where the volume excluded by a link is
vlo~.l = a P (7)
so that a appears in equation (6) as a numerical parameter. In the limit of
n > co, this leads to a mean square end to end distance
(r2> o = 0" 7 5 5n1~Pa °'4 (8)
The exponent of n is here exactly 6/5, giving ~/ (equation (5))=0"20, in
agreement with the lattice calculations.
For the purpose of this paper, it has been a s s u m e d that an equation of
the form (6) is valid also for finite values of n. Although this will not be
strictly true, it should suffice to indicate semi-quantitatively the conse-
quences of departure from Gaussian statistics.
For application to the theory of elasticity, the distribution is conveniently
expressed in terms of the configurational free energy of a chain whose ends
are fixed at two specified points, a distance r apart. For a chain obeying
Gaussian statistics, i.e. equation (1), this has the form
G = const. + ( 3 k T / 2 n l S ) r ~ (9)
If such a chain is deformed from an initial length r . to a final length r, the
increase of free energy is then
A G = ( 3 k T / 2 r i P ) (r = - r~) = ( 3 k T / 2 n P ) ~ ( h 2 - 1) (10)
where h is defined as r/r~.
For non-Gaussian chains, G will no longer be linear in k=; numerical
calculations have been reported 8 on the basis of Schatzki's work. If an
equation of the form (6) holds, (9) and (10) must be replaced by
G = const. + (1 "35/ni 2) (r - r*) 2 (11)
AG = (l . 3 5 k T / n P ) r ~ [()~ - b) 2 - (1 - b) 2] (12)
If equation (6) held exactly we should have further
r * = br~ = 0"87 Ia°2n °'~ (13)
and we m a y guess that this is the correct limit as n > c¢.
The mean value of r 2 has been obtained as a function of b by numerical
integration of
~ r a exp [ - ( 1 "35/nl 2) ( r - r*) 2] dr
(r~>0 = ° (14)
~ r ~ exp [ - ( 1 " 3 5 / n P ) ( r - r*) 2] dr
0
L . . b=O'8
4 ~ /
/70"6
..0
/ ..-'~~0'4
t~
,¢1
~ °o-"
I I I
0 1 2 3
a2
Figure /--Effect of parameter b on chain free energy
of the polymer. As a result of the chemical reaction the system now contains
a large number of reacted points, and these will be randomly distributed
in space. Each reacted point links together two of the original long mole-
cules, and can now be thought of as a junction point from which four chains
radiate. Most of these chains will terminate at some other junction point,
and it is therefore convenient to speak of the length of molecule comprised
between two junction points as a chain. A few chains will form a closed
loop, returning to the same junction point. A number of chains equal to
twice the original number of molecules will terminate in a free end. For
most purposes, we can ignore both closed loops and free ends, and regard
the structure as a perfect network.
When the body is deformed by the application of forces, the whole
network must respond, and will of course do so in such a way that the
increase of free energy is a minimum. It is frequently assumed that the,
network free energy is simply the sum of the free energies of the individual
chains. If these are Gaussian, and a representative chain changes its end to
end distance from ri to r, the resulting free energy increase will be given
by equation (10). To obtain an expression for the network free energy, we
have still to solve two problems: to evaluate ri; and to sum over all the
chains.
The simplest forms of theory put r~ =(rS>o =n/s, and thus obtain, for
the representative chain,
A G = 1.5 k T ()t s - 1) (18)
The essential assumption involved in the summation is that each chain
undergoes affine deformation, i.e. that its end to end distance changes pro-
portionally to the bulk dimensions in the direction in which the chain lies.
It then follows that if there are N chains in the network, and the total
deformation is described by the three principal strains ~,1, h2 and h3, the
total free energy of deformation is given by
AG = 0"5 N k T (hl + h~ + h~ - 3 ) (19)
Wall and Flory11 have argued that an additional term is required when
• 8
the deformation revolves a change of volume, to take account of the
combination of the chains into a network; they modify (19) to
AG = 0-5 N k T [hl + hl + hi - In (hi As h3) - 3] (20)
The identification of ~ with <r2>0 is based on the argument that any pair
of segments in the linear polymer will on average be at this separation.
When crosslinking occurs, the pair which form contiguous junction points
become relatively fixed in position, and therefore retain this separation.
This argument ignores a number of important considerations: (a) The
value of <r2)0 which should be used is that appropriate to the conditions of
crosslinking, which will typically involve a temperature much higher than
that of the subsequent deformation. Unless (r~>o is temperature-independent,
chains which are at their most probable lengths when formed will no
longer be so in the undeformed test piece used in a normal mechanical
test. (b) Unless all the crosslinks are formed simultaneously, the growing
fragments of network will tend to contract, thereby changing the statistics
377
G. G E E
and
iov
~,0i--,~r. , = k s - 1 = 2 jO CTqJ(lO
x_s
(25)
chain, and by h2 that of the other three chains (Figure 2). The problems
to be examined are: (a) the position of the junction point, and (b) the
magnitude of the force.
The free energy is given by
AG/C = (Xl - b) 2+ 3(X2 - b) 2 - 4(1 - b) 2 (27)
and geometrical considerations require
hl = (~AS- 2~1)~+ 8s2/9h (28)
The position of the junction point will be such that OG/Oht =0, the solution
to which is conveniently written in terms of y = AS- hi
379
G. GEE
~ ~(~:2,45)
tO Figure 3 - - D e p e n d e n c e
of AG on
XI at fixed h = 2 " 4 5
215
(ii) Load/elongation curves were evaluated for a range of values of
b and s. These are represented in Figure 4 in the form of the function
dp=fs-2(h-h-~) -1, while the departure from Gaussian behaviour is shown
in Figure 5 by plotting y/hs. It is easily seen, from the form of the equations,
that these functions do not depend on b and s independently, but only on
b/s. Thus while b will increase with dilution, its effect on the elastic
behaviour of a network is compensated by the increase in s. For h > 1, y / ~
shows a maximum at approximately 100 per cent elongation, representing
a three per cent departure from affine deformation for b/s=0"2. For the
same b/s, the increase in ~b from h = l is two per cent at h = 2 , increasing
to five per cent at h=3, and eight percent at ~ = 4 .
38O
THE PRESENT STATUS OF THE THEORY OF RUBBER ELASTICITY
-- b/s=O.033
2.6 _....-- 0.1
~ 0.2
~ ~ 0.25
2-4 0.333
0.4
(~22
2.0
I I , 1 I I,
1 2 3 4
0'05
0,2
01
0 0033
¢o
-0'05
-0"1 • , r ! , f 1
1 2 3 4
X
Figure5--Departure from affine deformation
/
/
//Expt
I I I,
0 0.5 1 l"b
1/~
broken lines represent equation (32). On the same figure are included two
curves replotted from Figure 5. Comparison cannot of course be exact,
since our model represents only a typical dement of the network, deformed
in a particular way. Nevertheless, two conclusions seem justified: (I) a
very large ratio b/s would be needed to produce any detectable change
in ~b; (2) even with a large ratio b/s, the highly characteristic fall of ~b from
h = 1 to h = 2 is not reproduced at all. In the light of these observations,
the suggestion made previously8, that the C~ term might be due at least
in part to the excluded volume, must be withdrawn.
It is more difficult to make any positive contribntion to the interpretation
of C2, more particularly since recent experimental work 19 has tended to
contradict earlier evidence that C2 does not vary widely. It may, however,
be worthwhile to call attention a g a i n 2°' 2t to the fact that the theoretical
treatment ignores completely the problem of molecular packing in the solid
state. This will greatly reduce the configurational entropy of the system, but
will only contribute to the observed force if the packing free energy changes
on deformation. DiMarzio ~2 has recently concluded, on the basis of an
admittedly crude analysis, that while this will indeed contribute to C~, by
itself it can account for no more than a small part of a typical value of
382
THE PRESENT STATUS OF THE THEORY OF RUBBER ELASTICITY
The importance of the correction term a/(h 3- 1) is obvious, but the fact
that the final column shows no systematic dependence on ~ suggests that
the dilation has been correctly estimated. Taken by itself, this evidence is
far from compelling, as it is easily shown that a modification of equation
(25) may change the figures in the last column without causing them to
depend on h. More convincing is the cumulative effect of a series of such
investigations2~-29in some of which an independent estimate of d In <r2>0/dT
383
G. G E E
Department o¢ Chemistry,
University of Manchester
(Received January 1966)
REFERENCES
1 See, for example, TRr~LO~, L. R. G. The Physics of Rubber Elasticity, Chapters
3 and 4. Oxford University Press: London, 1958.
384
T H E P R E S E N T STATUS O F T H E T H E O R Y O F R U B B E R ELASTICITY
385